Light-sensitive silver halide photographic materials

ABSTRACT

WHEREIN Ro, R1, R2, R3, R4, R5, R6, Y1, Y2, X and m are defined hereinafter, and compounds of the general formula   WHEREIN R8, R9, R10, L1, L2 and Y3 are defined hereinafter. There is provided a light-sensitive silver halide photographic material comprising at least one layer on a support which comprises a binder containing (i)light-sensitive silver halide grain particles characterized as exhibiting a high surfacesensitivity; (ii) at least one compound containing a Group VIII metal at a level of from 1 X 10 6 to 1 X 10 3 mol per 1 mol of said silver halide (iii) at least one optical sensitizer selected from the group consisting of compounds of the general formula

United States Patent 1 1 1111 3,890,154

Ohkubo et al. 1 June 17, 1975 1 1 LIGHT-SENSITIVE SILVER HALIDE PrimaryExaminer-J. Travis Brown PHOTOGRAPHIC MATERIALS Anorney, Agent, orFirm-Sughrue, Rothwell. Mion,

' M 'k 175 inventors: Kinji Ohkub;Junpe1Noguchi;

Kunioki Ohmura; Masanao Hinata, [57] ABSTRACT all of Kanagawa, Japan IThere is provided a hght-sensmve sliver halide photo- 1731 Assign: FujiPhmo graphic material comprising at least one layer on a Kanagawa, Japansupport which comprises a binder containing (i)light- [22] Filed; Mar.23, 1973 sensitive silver halide grain particles characterized asexhibiting a high surface-sensitivity; (ii) at least one [21] Appl3441401 compound containing a Group VIII metal at a level of RentedAppncation m from l X to l X l0" mol per 1 mol of said silver {63]continuuflommpan of Ser No ml 233 Dec 24 halide (iii) at least oneoptical sensitizer selected from 1970 abandoned the group consisting ofcompounds of the general for mula I i R" L; n l C=C1l-C ce-c li R(if'lm-l Foreign Application Priority Data wherein m 1. 2, 3, 4. 5.11. 1. 2. X n m are Dec. 24. 1969 Japan ..44-1o4009 defined hereinafter,and Compounds of the general Jan 9, 1970 Japan -002819 formula [52] US.Cl. 96/125; 96/108; 96/126; 96/137; 96/140 51} 1111. C1 G03c 1/08 F N s[53} Field of Search 96/l25, 126, 137, 140, i

96/108 N c=1d L =CY [56] References Cited 1 1 UNITED STATES PATENTS R C-N /C\\\ 5 2.912329 11/1959 Jones et a1. 96/137 0 3,206,313 9/1965 Porterct a1 96/108 1 3,672,901 6/1972 Ohkubo et al 96/108 R10 3,741,767 6/1973Baylis ct a1. 96/108 $761,266 9/1973 Milton r r 96/108 3,761,267 9/1973Gilman et a1. t 96/108 3,782,957 l/l974 Ohkubo et al 1. 96/l25 wherein RR R L,, L and Y, are defined h i FOREIGN PATENTS OR APPLICATIONS 801.2759/1958 United Kingdom...1............... 96/140 23 Claims, 1 DrawingFigure PATENTEBJUN 17 m5 M TRANSMITTANCE 550 400 450 560 a so '00 WAVELENGTH (nm) INVENTORS KINJI OHKUBO JUNPEI NOGUCHI KUNIOKI OHMURA MASANAOHINATA LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIALSCROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part application of our earlier co-pending applicationSer. No. 101,233 filed Dec. 24, 1970, now abandoned which claimspriority from Dec. 24, 1969 and Jan. 9, i970, respectively, based onJapanese Patent Applications 104009169 and 2819/70, respectively.

BACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates to photographic silver halide light sensitivematerials. More particularly, the present invention relates tophotographic silver halide light sensitive materials having highsensitivity to green light under flash exposure. The term flash exposureis defined hereinafter.

2 Description of the Prior Art The present age is one of information.Various systems have been developed to promote the speedy transmissionof information. For instance, press facsimile systems a speedilytransmit press manuscripts to distant places, high speedphototypesetting systems expedite printing and typesetting, and cathoderay tube (CRT) display systems represent speedily in letters of figuresthe information output of computers. With such equipment used for suchrapid information transmitting systems, a short time exposure of lessthan l/l00,000 of a second or especially about 1 1,000,000 of a secondis most often used. The demand for sensitive materials to be used forsuch equipment has in recent years been particularly high.

There are two types of light sources used in connection with these typesof equipment, viz., xenon flash lamps and cathode ray tubes. Of these,the one whose fluorescence has an especially short afterglow knowngenerally to be usable for flying spot, is used as the cathode ray tube.For instance, such fluorescent materials are called P-l l, "*P-lS," P-l6and P-24" and are used as the light source in question. It is known thatthe luminous distribution of spectral energy reaches a peak when P-l lreaches 460 nm. and when P-l6 reaches 385 nm. This peak corresponds tothe region of the spectral absorption characteristic of light sensitivesilver halides and hence does not need any optical sensitization. On theother hand, it is known that P-l5 has its maximum fluoroscent spectralenergy at 505 nm. and for P-24 at 520 nm. The sensitive materials forrecording images on CRT must therefore be given sensitivity to greenlight. On the other hand, a xenon flash lamp emits light over acomparatively broad spectral region. The light from the light sourcegives images on the sensitive materials through an optical systemcomposed ofa condenser lens, a negamatrix, a main lens, a prism. areflector or a deformation lens or other special lenses, or prisms. Thelight of short wave length is absorbed to a greater extent by the opticsin the path. As a result of the light reaching the sensitive material,the shorter wave length component of from ultraviolet to blue diminishesand the longer wave length component from the green becomes richer. Forthis reason, green sensitization is indispensable in order to enhancethe sensitivity of the sensitive material. The above-described afterglowof the fluorescence of a cathode ray tube ranges from l/l0,000,000 tol/100,000 of a second and with a xenon flash lamp also one of about thesame radiation period is used. In the present invention the short timeexposure of these two kinds of light sources described above isgenerically called flash exsposure.

The conventional sensitizer for green light shows markedly lower spectrosensitization under a flash exposure of l/l00,000 of a second or less incomparison with the result of a conventional exposure of l/l,000 ofasecond or longer. Specifically there is a fair indication of this trendwhere, in order to expedite after exposure the treatments such as fixingor stabilization, silver halide is partly or wholly composed of silverchloride, i.e., a silver chloride emulsion, a chlorobromide emulsion ora chloroiodobromide emulsion.

An object of this inventoin is to provide photographic sensitivematerials having high sensitivity to green light under flash exposure.

SUMMARY OF THE INVENTION This invention provides silver halide lightsensitive photographic materials comprising a support on which at leastone layer having in the binder (such as gelatin and the like) sensitivesilver halide grain particles characterized as exhibiting a high surfacesensitivity, at least one compound containing a Group VIII metal of theperiodic table at the ratio of from 10* to [0 mo] per 1 mol of silverhalide, and at least one optical sensitizer selected from the groupconsisting of compounds of the general formula:

wherein R represents a hydrogen atom or an alkyl group; wherein R and Reach represents a hydrogen atom, an alkyl, a substituted alkyl, anallyl, an aryl or an aralkyl group, in which at least one of R and R,must be a carboxyalkyl group or a sulfoalkyl group; wherein Y and Y eachrepresents an oxygen atom, a sulfur atom or a l-lR group in which R, isan alkyl group; wherein R R R and R each represents a hydrogen atom, ahalogen atom, an alkyl, a cyano, an alkoxy or an aryl group, when atleast one of R and R is an aryl group, R and R are not an aryl group;wherein X represents an anion, such as a halogen ion or a thiocyanateion; and wherein m is l or 2, in which an intramolecular salt is formedwhen m is l, and compounds of the general formula wherein R,,, R and Reach represents a hydrogen atom. an alkyl, a substituted alkyl, anallyl, or an aryl group; wherein Y represents an oxygen atom, a sulfuratom or a NR,, group, in which R is a hydrogen atom, an alkyl or an arylgroup; wherein L, and L each represents the atoms of a methine chain.

DESCRIPTION OF THE ACCOMPANYING DRAWINGS The accompanying drawing showsthe light transmittance of a glass filter V-YSO used in the examples inevaluating the effectiveness of the light sensitive photographicmaterialsv DETAILED DESCRIPTION OF THE INVENTION silverchloroiodobromide, can be used. The so-called preparation of thesensitive silver halide emulsion, that is, the preparing of the silverhalide crystal grains in the binder in a dispersive state, and makingthem grow into the proper crystal size thus preparing the silver halideemulsion, can be done by conventional techniquesv With respect to thelight sensitive silver halide particles employed in the presentinvention, it must be emphasized that these particles are characterizedas exhibiting a high surface sensitivity. Therefore, the silver halideparticles of this invention are quite different from particles of thecore shell type, which exhibit low surface sensitivity and high internalsensitivity.

The metals belonging to Group VIII of the periodic tables are iron,cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,platinum. Examples of the compounds containing these metals desirablyused in this invention contain a single salt, or a hexagonal complex,tetragonal complex, or square plane complex of an alkali metal orammonium such as ferrous sulfate (FeSO,.5H O); ferric chloride (FeClpotassium hexacyanoferrate (II)(K,,]Fe(CN) l ,3H O); potassiumhexacyanoferrate (lII)(K ]FeCN l); cobalt (ll) chloride (CoClzl; Cobalt(II) nitrate (Co[NO 6 H O); potassium hexacyanocobaltate (Ill) (K {Co(CNnickel (II) chloride (NICI .6H O); nickel (II) nitrate (Ni[N0;,] .6H O);ruthenium chloride (RuCl );potassium hexachlororuthenate (IV) (K RuCl6);rhodium (lll) chloride (RhCl .4H ammonium hexachlorohodate (III) (INH JRhC'I palladium nitrate (Pd[BO palladium bromide (PdBr potassiumhexachloropalladate (IV) (K PdCI potassium tetrathiocyanopalladate (II)(K Pd[CNS] osmium (II) chloride (OsCl iridium (III) chloride (lrCliridium (IV) chloride (lrCl iridium (III) bromide (lrBr .4- H O);iridium (IV) bromide (IrBr potassium hexachloroiridate (III) (K IrClpotassium hexachloroiridate (IV) (K lrCl ammonium hexachloroplatinate(IV) magma potassium hexachloroplatinate (IV) (K PtCI ammoniumhexabromoplatinate (IV) ((NH PtBr These metallic compounds of Group VIIIare used either singly or in combinations of two or more compoundstogether in the silver halide emulsion in a quantity corresponding from(0 mol to 10 mol, preferably 10 to 3 X 10", per l mol of silver halide.The addition of these compounds in the emulsion can be made suitably atvarious stages in the preparation, viz., at the formation of silverhalide grain particles in the preparation of silver halide emulsionadded either in the halide solution or in the dispersive gelatinsolution, or at the beginning of the ripening of the emulsion or atintermediate steps. Also, the compound can be added together with othervarious prior well known stabilizers, antifoggants, antibronzing agents,surface active agents, hardeners, plasticizers, matting agents,development accelerators or brightening agents and the like as desired,prior to the coating of the emulsion.

One of the optical sensitizers in the present invention is the compoundhaving the following general formula:

wherein R represents a hydrogen atom or an alkyl group having from 2 to3 carbon atoms, such as a methyl group, an ethyl group and the like;wherein R and R each represents hydrogen or an alkyl group having from Ito 4 carbon atoms, such as a methyl group, an ethyl group or propylgroup and the like, a substituted alkyl group of the type usually usedas an N- substituent of a cyanine dye such as a hydroxyalkyl group(e.g., B-hydroxethyl), an acetoxyalkyl group (e.g., ,B-acetoxyethyl), analkyl group having a carboxy group such as a carboxy-(alkoxy),, ,-alkylgroup wherein n is l or 2 (eg, carboxymethyl, B-carboxyethyl,y-carboxypropyl, 2-(2-carboxyethoxy) ethyl), an alkyl group having asulfo group such as a sulfo -(alkoxy),, ,-alkyl group wherein n is I, 2or 3, a hydroxysulfo- (alkoxy),, alkyl group wherein n is I or 2 or anacyloxysulfoalkyl group (e.g., flsulfoethyl, y-sulfopropyl,S-sulfobutyl, 2hydroxyl-l-sulfopropyl, 2-(3sulfopropoxy)ethyl,Z-acetoxy-l-sulfopropyl, 3-methoxy-2- (3-sulfopropoxy )propyl,2-]2-(3-sulfopropoxy) ethoxy]ethyl, 2-hydroxy-3-(3-sulfopropoxy)propyl,and the like, an aryl group such as phenyl group or an aralkyl group,but at least one of R and R is a carboxyalkyl group or a sulfoalkylgroup; wherein Y and Y each group but when at least one of R and R is anaryl are an oxygen atom. a sulfur atom or a N R group group then neitherR nor R is an aryl group; wherein in which R is an alkyl group havingfrom 1 to 3 carbon X is an anion such as a halogen ion, a thiocyanateion, atoms, such as a methyl group or an ethyl group and the sulfateion, sulphamate ion, perchlorate ion, p-toluene like; wherein R R R andR ea h re r t a h d 5 sulphonate ion, benzensulphonate ion. ethylsulphate gen atom, an alkyl gro h in f 1 1 3 carbon ion, or methylsulphate ion, and wherein m represents atoms, such as a methyl group oran ethyl group and the l or 2, in which an intramolecular salt is formedwhen like, a halogen atom (such as fluorine, chlorine, brom =1- mine), acyano group, an alkoxy group (such as a math Specific compounds of theseoptical sensitizers are oxy or an ethoxy group) or an aryl such as aphenyl 10 h w" 118 W I i N C H LH CH COOH C=CH-CH=CH- C Dye lXb I (cH2)3 coon c H where R,,, R, and R, each represents a hydrogen atom; analkyl group having from l to 8 carbon atoms, such Dye X m.pover 300C Cln as a methyl group, an ethyl group, a propyl group, a butyl group; asubstituted alkyl group of the type usu- 40 ally used as anN-substituent of a cyanine dye such as a carboxyalkyl group, (e.g., acarboxymethyl group), a hydroxyalkyl group (e.g., a B-hydroxyethylgroup), a sulfoalkyl group (e.g., a B-sulfoethyl group, a 'y-sulfopropylgroup); an ally] group; or an aryl group such as 45 a phenyl group, asubstituted phenyl group (for example, substituted with a halogen atome.g., a chlorine atom, an alkyl group and the like); wherein Y is anoxygen atom, a sulfur atom or a N-R group, in which R is a hydrogenatom, an alkyl group having from I 50 to 8 carbon atoms, or an arylgroup (e.g., a phenyl group); wherein L, and L in each a methine chain(e.g., =CH-, =C(alkyl); =C(aryl wherein examples of the alkyl group andthe aryl group are a methyl group and a phenyl group, respectively).

Specific compounds of these sensitizers are as follows:

N N-CH i CH in c s 45C N p-2 c c c H o s Dye xvn Dye XVIII DyaXlX c C HC =C| C 4 \T/ C 2 H These sensitizers are described, for example, in theBritish Pat. No. 801,275 and the synthesis of these sen sitizers is wellknown by reference to the patent cited above and also to the relevanttechnical literature.

These optical sensitizers are applied, either singly or in combinationof two or more, at a ratio of from l0 to 10 mol, preferably 10" to 3 X10 mol, per l mol of silver halide in the silver halide emulsion. Thisaddition of the optical sensitizer to the emulsion is the same as withthe metal compounds above described. The addition into the emulsion canbe made either simulta neously with the metal compound, or separately.The sequence of the addition is immaterial.

Thus, it can be seen that the silver halide lightsensitive photographicmaterial can be made essentially in the same manner as usual except thatthe above metal compound and optical sensitizer are added and thesensitive material thus prepared can, after flash exposure, be developedand fixed in a conventional manner. Also, the material can be treated ina manner known generally as the diffusion transfer process. Or, byadding beforehand an ample quantity of the developing agent in thelight-sensitive layer, the develop ment can be treated by the generallyknown activator development process (a process by which thelightsensitive material containing a developing agent is developed in asolution which does not contain a develop ing agent and in which onlyalkaline material is dis solved).

It has been observed that with light-sensitive materi als containing theabove-described metal compounds but not containing the opticalsensitizers, the sensitivity to the green light is not obtained,although, in some cases, their sensitivity to blue light improves. Onthe other hand, it is recognized that in the case of the sensitivematerial not containing the metal compounds but containing only theoptical sensitizers, the green light mp. 290C sensitivity is not veryhigh. However, by using these two types of materials simultaneously thegreen light sensitivity in the flash exposure can be markedly improved.

Specifically, with a silver chloride emulsion, a silver chlorobromideemulsion, or a silver chlorobromoiodide emulsion, if the abovesensitizer is used alone, a considerable lowering of the efficiency ofspectral sensitization in the flash exposure is experienced. For suchemulsions the present invention is particularly useful.

It has long been known that the metal compounds described above showvarious noticeable effects, and as is shown in US. Pat. No. 2,448,060,when hexahalogenoruthenium (lll) acid salts, hexahalogenorhodium (IV)acid salts, hexahalogeno osmium (IV) acid salts, hexahalogenoiridium(IV) acid salts, or hexahalogenoplatinum (lV) acid salts are added to asilver halide emulsion at the time of ripening, the sensitivity of thisemulsion increases. And further, as is disclosed in US. Pat. No.2,566,745, when these compounds are added additionally to the silverhalide emulsion the stability of the sensitive material under hightemperatures and humidity improves, and further, as is disclosed in US.Pat. No. 2,517,54], potassium hexacyanocobaltate (Ill) and in FIATReport No. 360 rhodium trichlo ride, when this compound is added to asilver halide emulsion the contrast of the image obtained from thisemulsion increases.

We have found that the iron compounds make the contrast of the emulsionhigher.

The compounds of Group Vlll elements in the periodic table are addedsolely for the objects of this invention, but they can also be used toobtain various photo graphic effects as described above at the sametime. Also, as is shown in British Pat. No. 570,393, one can apply themethod of increasing the sensitivity of the emulsion by adding the metalcompounds at the time of ripening. In other words, when used as asensitizer or as a stabilizer or as an additive for increasing contrast,the effect of sensitization to green light is displayed if the abovedyes are used together. The efficiency which the usual techniques aim atis not hindered.

The present invention will be illustrated in greater detail by thefollowing examples.

EXAMPLE I An ordinary acid process silver chlorobromide cmulsion wasprepared (containing 30 mol 71 AgBr) not containing the compoundscontaining metals of Group Vlll of the periodic table (hereinaftersimply called metal compounds) and by the same method an emulsion wasprepared. and at the time of forming the silver halide grains, ammoniumhexachlororhodate (Ill) was added in a quantity equivalent to 7 X l molper silver halide 1 mol, and at the after-ripening step, potassiumhexachloroplatinate (IV) was added in a quantity corresponding 2 X 10'mol per silver halide l mol and the thus prepared emulsion was similarin sensitivity to the conventional emulsion. Each of these 2 emulsionswas divided into two parts. One part was not dye-sensitized. To theother was added Dye l in a quantity of 4 X mol per 1 mol of silverhalide in the emulsion. Next, formaldehyde was added to each of these ina quantity of 2.5 per IOO g of gelatin of the emulsion, and then eachwas applied to a photographic baryta paper.

Using an EG & G Sensitometer Mark Vll and through a colored glass filterV-YSO (made by Tokyo Shibaura Electric Co, Ltd.) and an optical wedge,the above described samples were each given exposures of 1/100 and ofl/l,000,000 of a second. As is shown in the drawing, the colored glassfilter V-Y50 (made by Tokyo Shibaura Electric Co., Ltd.) absorbs thelight corresponding to the sensitive spectral region of the unsensitizedsilver halide and transmits only the light corresponding to theoptically sensitized region of greater than about 500 nm. The exposedsamples were developed at C for 2 seconds in the following developer:

NMethyl-para-aminophenol 2 g Sodium Sulfite, Anhydrous 30 g Hydroquinone7 g Sodium Carbonate (Monohydrate) 53 g Potassium Bromide 1.5 g Water upto l liter l/l00th lll .0O0.000th Second Second Exposure ExposureControl Emulsion 0 0 Group Vlll Metal Only 0 0 Dye l Only 4.9 0.9 GroupVlll Metal Dye l 4.6 3.2

it was observed that by using the rhodate compound, the platinatecompound and Dye (l) the green light sensitivity to flash exposure wasincreased.

EXAMPLE 2 A silver chlorobromide emulsion (containing 50 mol percentAgBr) was prepared in a neutral medium by a well known process and whichdoes not contain the compounds of a Group Vlll metal of the periodictable (hereinafter simply called metal compounds), and one was alsoprepared by adding hexachlororhodate (III) in a quantity of 3 X 10 molper 1 mol of silver halide in the above emulsion at the time of theformation of the silver halide grains, then further after ripeningpotassium chloroplatinate was added in a quantity of 2 X 10' mol persilver halide 1 mol. The thus prepared emulsion had about the sensitiveas the abovedescribed emulsion. These two emulsions were each divided intwo parts. One was left intact.

To the other part was added the Dye X in a quantity of6 X 10* mol per lmol of silver halide in the emulsion. Next, formaldehyde was added toeach of these in the quantity of 2.5 g per g of gelatin of the emulsion,and the emulsion was applied to a photographic baryta paper.

The green light sensitivity was measured for the sample thus obtained inthe manner as described in Example l and the following results wereobtained.

It was observed that by using simultaneously the rho date salt, theplatinate salt and Dye X, the green light sensitivity to the flashexposure was increased.

EXAMPLE 3 A silver chlorobromide emulsion (AgCl 50 mol percent, AgBr 50mol percent) which does not contain the metal compounds of thisinvention was prepared in a neutral medium in a conventional manner.

Next, by the same method, at the formation of the silver halide grains,3 X 10" mol per 1 mol of silver halide of ammonium hexachlororhodate wasadded to the emulsion, and then after ripening, platinum (IV) chloridein the quantity of 2 X 10 mol per silver halide 1 mol was added toprepare an emulsion having a sensitivity similar to that of the emulsionwithout the metal compounds. To each of these emulsions, as in ExampleI, Dye [V at a level of 2 X lo mol per 1 mol of silver halide wasfurther added. In addition, 2.5g of formaldehyde was added per 100g ofgelatin, and the emulsion was applied to a photographic baryta paper.The optical sensitization of the sample obtained was measured in thesame manner as described in Example 1. The results obtained are shown inthe following table.

In this case the effect of using the rhodate compound, the platinatesalt and Dye IV together was observed.

EXAMPLE 4 A silver chlorobromide emulsion (AgBr 70 mol percent, AgCl 30mol percent) which does not contain the metal compounds of thisinvention was prepared in an ammonium alkali medium in a conventionalmanner. Next, in the same manner potassium hexacyanoferrate (III) wasadded in a quantity of l X 10 mol per 1 mol of silver halide of theemulsion at the formation of silver halide grains. To these twoemulsions Dye III was added in quantity of2 X mol per 1 mol of thesilver halide.

Further, formaldehyde in a quantity of 2.5g per 100g of gelatin wasadded and the emulsion was applied to a photographic baryta paper. Thesensitivity to green light of the samples thus obtained was measured inthe same manner as described in Example I. The results obtained areshown in the table below.

l/lOOth l/l,000.000th In this case the combined effect of a Group VIIImetal compound and Dye III was observed.

EXAMPLE 5 A silver chlorobromoiodide emulsion (AgBr 70 mol percent, AgCl29 mol percent, Agl I mol percent) which does not contain the metalcompounds of this invention was prepared in an ammonium alkali mediumusing a conventional method. Next, using the same pro cedure, 4 X I0 molper I mol of silver halide of potassium hexacyanoferrate (III), 6 X 10mol per 1 mol of silver halide of potassium hexachloroiridate (IV), 3X10" mol per 1 mol of silver halide of ammonium hexachlororhodate (III)were added at the time of formation of the silver halide grains, andagain at the afterripening 3 X l0 mol per l mol of silver halide ofchloroauric acid was added, and prepared an emulsion having asensitivity similar to that of the ordinary sensitivity.

To this emulsion as well as to the emulsion described above, Dye III ina quantity of 6 X 10 mol per silver halide 1 mol was added. Further,formaldehyde 2.5g per 100g of gelatin was added and the emulsion wasapplied to a photographic baryta paper. The green light sensitivity ofthis sample was then measured in the same manner as in Example I. Theresults obtained are shown in the table below.

Also, in this case the effect of the joint application of the Group VIIImetal salt and Dye III was observed.

EXAMPLE 6 To the emulsion as used in Example 3 Dye VI was addedcorresponding to a quantity of 8 X IO mol per silver halide I mol, andthis sample was tested in the same manner as described in Example I. Theresults obtained are shown in the table below.

In this case also, the effect of the combined treatment of Group VIIImetal salt and Dye VI was observed.

EXAMPLE 7 A silver chlorobromide emulsion (AgCl 50 mol percent, AgBr 50mol percent) which does not contain the metal compounds of thisinvention was prepared in an ammonium alkali medium in a conventionalmanner. Next, using the same procedure, at the formation of the silverhalide grains, I X 10 mol per 1 mol of silver halide of potassiumhexacyanoferrate (III) was added and the emulsion having a sensitivitysimilar to that of the emulsion not containing metal compounds wasobtained. To each of these emulsions, as described in Example 1, DyeVIII was added in a quantity of4 X 10* mol per 1 mol of silver halide.Further, formaldehyde in a quantity of 2.5g per lOOg of gelatin wasadded, and the emulsion was applied to a photographic baryta paper. Thesensitivity to green light of the thus obtained samples was measuredusing the same method as used in Example 1 and the following resultswere obtained.

In this case also, the combined effect of the ferrate and the Dye VIIIwas observed.

EXAMPLE 8 A chloroiodobromide silver halide emulsion (AgBr mol percent,AgCl 29 mol percent, Agl I mol percent) was prepared not containingmetallic compounds of the present invention, using the conventionalammonium method. To an emulsion of the same composition we re added atthe formation of silver halide grain particles, 4 X I0 mol potassiumhexacyanoferrate (III) 6 X 1O- mol potassium hexachloroirridate (IV), 3X IO" ammonium hexachlororhodate (III) per l mol silver halide in theemulsion, and then, at the after-ripening, 3 X IO per l mol of silverhalide of chloroauric acid was added. A sensitivity similar to that ofthe abovedescribed ordinary emulsion was obtained.

To these emulsions was added Dye VII in a quantity corresponding to 2 XI0 mol per silver halide I mol. Again, to these emulsions was addedformaldehyde in a quantity of 2.5g per IOOg of gelatin to prepare aphotographic emulsion which was applied to a photographic baryta paper.The green light sensitivity of the sample was measured in the samemanner as in Example l. The results obtained are shown in the tablebelow.

In this instance also the effect of the combined use of the Group Vlllmetal salt and Dye Vll was observed.

EXAMPLE 9 Dye XV] was added to an emulsion which was the same as used inExample 3 in a quantity of 2 X mol per l mol of silver halide. Theemulsion was then treated the same as in Example 3 and tested in thesame way as Example I.

l {100th l/l ,000.000th Second Second Exposure Exposure Control Emulsion0 0 Group Vlll Metal Only 0 l] Dye XVI Only l3) Group Vlll Metal Dye XVI89 79 In this case also the effect of the combined use of the Group Vlllmetal salt and Dye XVI was observed.

In all the foregoing Examples, the silver halide particles employed werethose which exhibited a homogeneous structure and further, exhibited ahigh surface sensitivity.

While the present invention has been adequately described in theforegoing specification and Examples included therein, it is readilyapparent that various changes and modifications can be made to the samewithout departing from the spirit and scope thereof.

What is claimed is:

l. A light-sensitive silver halide photographic material comprising atleast one layer having high sensitivity to green light under flashexposure on a support which comprises an emulsion consisting essentiallyof:

l. a binder,

2. light-sensitive silver halide grain particles of homogeneousstructure exhibiting high surface sensitivity, compared to core-shelltype particles,

3. at least one simple salt or complex salt of a Group Vlll metalselected from the group consisting of iron, cobalt, nickel, ruthenium,rhodium, palladium, osmium, iridium and platinum, and 4. at least oneoptical sensitizer selected from the group consisting of compounds ofthe general forwherein R is a member selected from the group consistingof a hydrogen atom and an alkyl group; wherein R and R each represents amember selected from the group consisting of a hydrogen atom, an alkylgroup of from 1 to 4 carbon atoms, a substituted alkyl group selectedfrom the group consisting of a hydroxyalkyl group, an acetoxyalkylgroup, an alkyl group having a carboxy group and an alkyl group having asulfo group, an ally] group, an aryl group, and an aralkyl group, inwhich at least one of R and R must be selected from the group consistingof a carboxyalkyl group and a sulfoalkyl group; wherein Y and Y each isselected from the group consisting of an oxygen atom, a sulfur atom, anda =NR group, in which R represents an alkyl group, wherein R R R and Reach is selected from the group consisting of a hydrogen atom, a halogenatom, an alkyl group, a cyano group, an alkoxy group, and an aryl group,in which if at least one R and R is an aryl group, then R and R,,- arenot an aryl group; wherein X represents an anion selected from the groupconsisting ofa halogen ion and a thioeyanate iron; and wherein mrepresents an integer of 1 or 2, in which an intramolecular salt isformed if m is 1; and compounds of the formula:

R o s wherein R R and R each represents a member selected from the groupconsisting of a hydrogen atom, an alkyl group of from I to 8 carbonatoms, a substituted alkyl group selected from the group consisting of acarboxyalkyl group, a hydroxyalkyl group and a sulfoalkyl group, whereinY is a member selected from the group consisting of an oxygen atom, asulfur atom, and a =NR group in which R is a member selected from thegroup consisting of a hydrogen atom, an alkyl group, and an aryl group,and wherein L and L each represents a methine chain.

2. The light-sensitive silver halide photographic material of claim 1,wherein said binders are selected from the group consisting of gelatin,polyvinyl alcohol, polyvinyl pyrrolidone, sodium alginate, carboxymethylcellulose and mixtures thereof.

3. The light-sensitive silver halide photographic material of claim 1,wherein said support is selected from the group consisting of glass,metal, wood, baryta paper, cellulose acetate film and polyester film.

4. The light-sensitive silver halide photographic material of claim 1,where the aryl group is selected from the group consisting of a phenylgroup and a substituted phenyl group whose substituents are selectedfrom the group consisting of a halogen atom and an alkyl group.

5. The light-sensitive silver halide photographic material of claim I,wherein said optical sensitizers are selected from the group consistingof 5.5',o-trichlorol.l '.3-triethyl-3' l 3carhoxypropyl l-henzimidazolecarhocyanine iodide and F-allyl-S-E 2-( l-ethyl-4-methyl-tetrazolylidene lcthylidenc lrhodamine.

6. The light'scnsitive silver halide photographic material of claim I,wherein said sensitizer is used at a level of from l X 10 to l X 10""mol per 1 mol ot said silver halide.

7. The light-sensitive silver halide photographic material of claim I,wherein said compound containing a Group VIII metal is potassiumhexacyanoferrate (Ill) and wherein said optical sensitizer is5,5',6-trichloro- I ,l ',3-triethyl-3-( 3carhox vpropyl)-benzimidazolecarhocyanine iodide,

8. The light'sensitive silver halide photographic material of claim 1,wherein said compound containing a Group VIII metal is ammoniumhexachloro rhodate (Ill) and wherein said optical scnsitizer is 5,5',6-trichloro-l ,l ',3-triethyl-3'-( 3-carboxypropyl)-benzimidazolo-carbocyanine iodide.

9. The light-sensitive silver halide photographic material of claim I,wherein said compound containing a Group VIII metal is potassiumhexachloroiridate (IV) and wherein said optical sensitizer isS,5',6-trichlorol,l ,3-t riethyl-3 3-carboxypropyl)-benzimidazolocarbocyanine iodide.

10. The light-sensitive silver halide photographic material of claim 1,wherein said compound containing a Group VIII metal is potassiumhexacyanoferrate (III) and wherein said optical sensitizer is3-allyl-S-[2-( lethyl-4-methyl-tetrazolylidene)-ethylidenelrhodanine.

11. The lightsensitive silver halide photographic material of claim I,wherein said compound containing a Group VIII metal is ammoniumhexachlororhodate (Ill) and wherein said optical sensitizer is3'allyl-5-(2- (l-ethyl-4-methyl-tetrazolylideneJ-ethylidenelrhodanine.

12. The light-sensitive silver halide photographic material of claim 1,wherein said compound containing a Group VIII metal is potassiumhexachloroiridate (IV) and wherein said optical sensitizer is3-allyl-5-l2-(lethyl4-methyl-tetrazolyiidene)-ethylidenelrhodanine.

IS. The light-sensitive silver halide photographic ma Combi nationSystem No The Simple or Complex Salt terial of claim I, wherein said Rrepresents a member selected from the group consisting of a methyl groupand an ethyl group; wherein R represents a member selected from thegroup consisting of a methyl group and an ethyl group; and wherein R R Rand R each represents a member selected from the group consisting olamethyl group, an ethyl group, a chlorine atom, a bromine atom, afluorine atom, a methoxy group, an ethoxy group, and a phenyl group.

14. The |ight-sensitive silver halide photographic material ofclaim 1,wherein said complex salt is a member selected from the group consistingof a hexagonal com plex salt, a tetragonal complex salt, and asquare-plane complex salt.

15. The light-sensitive silver halide photographic material of claim 14,wherein said complex salt is an alkali metal or ammonium salt selectedfrom the group consisting of hexacyanoferrate (ll), hexacyanoferrate(III hexachloroiridate (Ill).

16. The light-sensitive silver halide photographic material of claim 1,wherein said simple salts are rhodium (Ill) halide or iridium (IV)halide.

17. The light-sensitive silver halide photographic ma terial of claim 4,wherein the alkyl group having a carboxy group in R and R is acarboxy-(alkoxy),, ,-alkyl group wherein n is I or 2; wherein the alkylgroup having a sulfo group in R and R is selected from a sulfo(alkoxy),, -alkyl group (rt-=1, 2 or 3), a hydroxy sulfo'(alkoxy),,,-alkyl group (n=1 or 2) and an acyloxy-sulfo group.

18. The light-sensitive silver halide photographic material of claim 1,wherein the substituted alkyl group in R and R is selected from thegroup consisting of a betahydroxyethyl group, a beta-acetoxyethyl group,a carboxymethyl group, a beta-carboxyethyl group, a gamma-carboxypropylgroup, a 2-(2-carboxyethox y)ethyl group, a beta-sulfoethyl group, agammasulfopropyl group, a delta-sulfobutyl group, aZ-hydroxy-l-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, aZ-acetoxy-I-sulfopropyl group, a 3- methoxy-2-(3-sulfopropoxy)propylgroup, a 2-[2-(3- sulfopropoxyJethoxy]ethy] group and a 2-hydroxy-3-(3-sulfopropoxy)-propyl group; wherein the substituted alkyl group in RR and R is selected from the group consisting of a carboxymethyl group,a betahydroxyethyl group, a beta-sulfoethyl group and agamma-sulfopropyl group.

19. The light-sensitive silver halide photographic material of claim 1wherein the optical sensitizer and the simple or complex salt isselected from the following combination systems:

The Optical Sensitizer l Ammonium hexachlororhodate (III) Potassiumhexachoroplatinate (IV) N N CH, 2 do.

? CIHS (ontinued Combination System No The Simple or Complex Salt TheOptical Sensitizer 3 Ammonium hexuchlororhodute (Ill) 32 H 5 Platinum(IV) chloride y C] C=CH-CH=CH-C (9 N N S I I 2 5 fla s 4 Potassiumhexacyanoi 5 ferrule (III) c] C=CH-CH=CH-C (9n gv C I Potassiumhexacyano- 5 ferrute (Ill) Potassium hexachloroiridate (IV) Ammoniumhexaclorodo. rhodate (Ill) C2H5 6 The same as Nov 1 h C] g): C-CH-cH=cH-c n v 2s cu cu coou H 7 Potassium hexacyano- 2 H 5 c] femmmn :IQcH-GcH-c H 3 co N N 9 C H (CH $O 8 The same as No. 5 :2 5

C=CH-CH:CH-Ci@:\ NC t d N c1 l 2 5 CH CH CH COOH N N CH 9 The same asNo. 3 If C,H,, N

CH,CH=CH,

20. The light-sensitive silver halide photographic maprises exposing toa flash light the silver halide phototerial of claim 1, wherein flashexposure is exposure to the afterglow of the fluorescence of a cathoderay tube or a xenon flash lamp for time ranging from l/l0,000,000 of asecond to 1/l00,000 of a second.

21. A photographic recording process which comgraphic materialcomprising at least one layer having high sensitivity to green lightunder flash exposure on a support which comprises an emulsion consistingessentially of:

1. a binder,

2. light-sensitive silver halide grain particles of homo geneousstructure exhibiting high surface sensitivity, compared to core-shelltype particles.

3. at least one simple salt or complex salt of a Group VIII metalselected from the group consisting of iron, cobalt, nickel, ruthenium,rhodium, palladium, osmium, iridium and platinum, and

4 at least one optical sensitizer selected from the group consisting ofcompounds of the general for mula:

wherein R is a member selected from the group con sisting of a hydrogenatom and an alkyl group; wherein R and R each represents a memberselected from the group consisting of a hydrogen atom, an alkyl group offrom 1 to 4 carbon atoms, a substituted alkyl group selected from thegroup consisting of a hydroxyalkyl group, and acetoxyalkyl group, analkyl group having a carboxy group and an alkyl group having a sulfurgroup, an ally] group, an aryl group, and an aralkyl group, in which atleast one of R and R must be selected from the group consisting of acarboxyalkyl group and a sulfoalkyl group; wherein Y, and Y2 each isselected from the group consisting of an oxygen atom, a sulfur atom, anda =l\lR group, in which R represents an alkyl group wherein R R R and Reach is selected from the group consisting of a hydrogen atom, a halogenatom, an alkyl group, a cyano group, an alkoxy group, and an aryl group,in which if at least one R 3 and R is an aryl group, then R and R arenot an aryl group; wherein X represents an anion selected from the groupconsisting of a halogen ion and thiocyanate ion, and wherein mrepresents an integer of l or 2, in which an intramolecular salt isformed if m is l; and compounds of the formula:

A] N R8 "w I Y l 2 C 3 N l C C R O4 S wherein R R and R each representsa member selected from the group consisting of a hydrogen atom, an alkylgroup of from 1 to 8 carbon atoms, a substituted alkyl group selectedfrom the group consisting of a carboxyalkyl group, a hydroxyalkyl groupand a sulfoalkyl group, wherein Y is a member selected from the groupconslisting of an oxygen atom, a sulfur atom, and a =NR group in which Ris a member selected from the group consisting of a hydrogen atom, analkyl group, and an aryl group; and wherein L, and L each represents amethine chain, said exposing being for a time shorter than 1 X 10seconds, and thereafter developing said photographic material.

22. The photographic recording process of claim 20 wherein thephotographic material is exposed to a flash light for a time of at mostl X l0" seconds.

23. The photographic recording process as claimed in claim 20 whereinthe light-sensitive silver halide particles are formed by a processwhich comprises forming silver halide precipitates, and further whereina salt of a Group VIII metal is added at the stage of forming saidsilver halide precipitate.

1. A LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL COMPRISING ATLEAST ONE LAYER HAVING HIGH SENSITIVITY TO GREEN LIGHT UNDER FLASHEXPOSURE ON A SUPOORT WHICH COMPRISES AN EMULSION CONSISTING ESSENTIALLYOF,
 1. A BINDER,
 2. The light-sensitive silver halide photographicmaterial of claim 1, wherein said binders are selected from the groupconsisting of gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, sodiumalginate, carboxymethyl cellulose and mixtures thereof. 2.light-sensitive silver halide grain particles of homogeneous structureexhibiting high surface sensitivity, compared to core-shell typeparticles,
 2. light-sensitive silver halide grain particles ofhomogeneous structure exhibiting high surface sensitivity, compared tocore-shell type particles,
 2. LIGHT-SENSITIVE SILVER HALIDE KGRAINPARTICLES OF HOMOGENEOUS STRUCTURE EXHIBITING HIGH SURFACE SENSITIVITY,COMPARED TO CORE-SHELL TYPE PARTICLES,
 3. at least one simple salt orcomplex salt of a Group VIII metal selected from the group consisting ofiron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium andplatinum, and
 3. The light-sensitive silver halide photographic materialof claim 1, wherein said support is selected from the group consistingof glass, metal, wood, baryta paper, cellulose acetate film andpolyester film.
 3. at least one simple salt or complex salt of a GroupVIII metal selected from the group consisting of iron, cobalt, nickel,ruthenium, rhodium, palladium, osmium, iridium and platinum, and
 3. ATLEAST ONE SIMPLE SALT OR COMPLEX SALT OF A GROUP VIII METAL SELECTEDFROM THE GROUP CONSISTING OF IRON, COBALT, NICKEL, RUTHENIUM, RHODIUM,PALLADIUM, ISNUYNM IRIDIUM AND PLATINUM, AND
 4. LEAST ONE OPTICALSENISITIZER SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THEGENERAL FORMULA:
 4. at least one optical sensitizer selected from thegroup consisting of compounds of the general formula:
 4. at least oneoptical sensitizer selected from the group consisting of compounds ofthe general formula:
 4. The light-sensitive silver halide photographicmaterial of claim 1, where the aryl group is selected from the groupconsisting of a phenyl group and a substituted phenyl group whosesubstituents are selected from the group consisting of a halogen atomand an alkyl group.
 5. The light-sensitive silver halide photographicmaterial of claim 1, wherein said optical sensitizers are selected fromthe group consisting of5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazole-carbocyanine iodide and3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)ethylidene)-rhodamine. 6.The light-sensitive silver halide photographic material of claim 1,wherein said sensitizer is used at a level of from 1 X 10 2 to 1 X 10 5mol per 1 mol of said silver halide.
 7. The light-sensitive Silverhalide photographic material of claim 1, wherein said compoundcontaining a Group VIII metal is potassium hexacyanoferrate (III) andwherein said optical sensitizer is5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazole-carbocyanine iodide.
 8. The light-sensitive silver halide photographicmaterial of claim 1, wherein said compound containing a Group VIII metalis ammonium hexachloro rhodate (III) and wherein said optical sensitizeris5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazolo-carbocyanine iodide.
 9. The light-sensitive silver halide photographicmaterial of claim 1, wherein said compound containing a Group VIII metalis potassium hexachloroiridate (IV) and wherein said optical sensitizeris5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazolo-carbocyanine iodide.
 10. The light-sensitive silver halide photographicmaterial of claim 1, wherein said compound containing a Group VIII metalis potassium hexacyanoferrate (III) and wherein said optical sensitizeris3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)-ethylidene)-rhodanine.11. The light-sensitive silver halide photographic material of claim 1,wherein said compound containing a Group VIII metal is ammoniumhexachlororhodate (III) and wherein said optical sensitizer is3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)-ethylidene)-rhodanine.12. The light-sensitive silver halide photographic material of claim 1,wherein said compound containing a Group VIII metal is potassiumhexachloroiridate (IV) and wherein said optical sensitizer is3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)-ethylidene)-rhodanine.13. The light-sensitive silver halide photographic material of claim 1,wherein said R0 represents a member selected from the group consistingof a methyl group and an ethyl group; wherein R7 represents a memberselected from the group consisting of a methyl group and an ethyl group;and wherein R3, R4, R5 and R6 each represents a member selected from thegroup consisting of a methyl group, an ethyl group, a chlorine atom, abromine atom, a fluorine atom, a methoxy group, an ethoxy group, and aphenyl group.
 14. The light-sensitive silver halide photographicmaterial of claim 1, wherein said complex salt is a member selected fromthe group consisting of a hexagonal complex salt, a tetragonal complexsalt, and a square-plane complex salt.
 15. The light-sensitive silverhalide photographic material of claim 14, wherein said complex salt isan alkali metal or ammonium salt selected from the group consisting ofhexacyanoferrate (II), hexacyanoferrate (III), hexachloroiridate (III).16. The light-sensitive silver halide photographic material of claim 1,wherein said simple salts are rhodium (III) halide or iridium (IV)halide.
 17. The light-sensitive silver halide photographic material ofclaim 4, wherein the alkyl group having a carboxy group in R1 and R2 isa carboxy-(alkoxy)n 1-alkyl group wherein n is 1 or 2; wherein the alkylgroup having a sulfo group in R1 and R2 is selected from asulfo-(alkoxy)n 1-alkyl group (n 1, 2 or 3), a hydroxy-sulfo-(alkoxy)n1-alkyl group (n 1 or 2) and an acyloxy-sulfo group.
 18. Thelight-sensitive silver halide photographic material of claim 1, whereinthe substituted alkyl group in R1 and R2 is selected from the groupconsisting of a beta-hydroxyethyl group, a beta-acetoxyethyl group, acarboxymethyl group, a beta-carboxyethyl group, a gamma-carboxypropylgroup, a 2-(2-carboxyethoxy)ethyl group, a beta-sulfoethyl group, agamma-sulfopropyl group, a delta-sulfobUtyl group, a2-hydroxy-1-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, a2-acetoxy-1-sulfopropyl group, a 3-methoxy-2-(3-sulfopropoxy)propylgroup, a 2-(2-(3-sulfopropoxy)ethoxy)ethyl group and a2-hydroxy-3-(3-sulfopropoxy)-propyl group; wherein the substituted alkylgroup in R8, R9 and R10 is selected from the group consisting of acarboxymethyl group, a beta-hydroxyethyl group, a beta-sulfoethyl groupand a gamma-sulfopropyl group.
 19. The light-sensitive silver halidephotographic material of claim 1 wherein the optical sensitizer and thesimple or complex salt is selected from the following combinationsystems:
 20. The light-sensitive silver halide photographic material ofclaim 1, wherein flash exposure is exposure to the afterglow of thefluorescence of a cathode ray tube or a xenon flash lamp for timeranging from 1/10,000,000 of a second to 1/100,000 of a second.
 21. Aphotographic recording process which comprises exposing to a flash lightthe silver halide photographic material comprising at least one layerhaving high sensitivity to green light under flash exposure on a supportwhich comprises an emulsion consisting essentially of:
 22. Thephotographic recording process of claim 20 wherein the photographicmaterial is exposed to a flash light for a time of at most 1 X 10 7seconds.
 23. The photographic recording process as claimed in claim 20wherein the light-sensitive silver halide particles are formed by aprocess which comprises forming silver halide precipitates, and furtherwherein a salt of a Group VIII metal is added at the stage of formingsaid silver halide precipitate.